CN112300444B - Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber - Google Patents

Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber Download PDF

Info

Publication number
CN112300444B
CN112300444B CN202011213695.3A CN202011213695A CN112300444B CN 112300444 B CN112300444 B CN 112300444B CN 202011213695 A CN202011213695 A CN 202011213695A CN 112300444 B CN112300444 B CN 112300444B
Authority
CN
China
Prior art keywords
nano
butadiene rubber
styrene butadiene
heat
dual
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011213695.3A
Other languages
Chinese (zh)
Other versions
CN112300444A (en
Inventor
金永中
李裕铭
何刚
房勇
陈建
附青山
谭苏芸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University of Science and Engineering
Original Assignee
Sichuan University of Science and Engineering
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University of Science and Engineering filed Critical Sichuan University of Science and Engineering
Priority to CN202011213695.3A priority Critical patent/CN112300444B/en
Publication of CN112300444A publication Critical patent/CN112300444A/en
Application granted granted Critical
Publication of CN112300444B publication Critical patent/CN112300444B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides a dual-phase nano filler, a preparation method thereof and application thereof in styrene butadiene rubber, and relates to the field of rubber processing. The dual-phase nano filler provided by the invention comprises spiral nano carbon fibers and nano TiO discretely loaded on the surfaces of the spiral nano carbon fibers2(ii) a The nano TiO2Is in rutile type. In the present invention, the spiral filamentous nanocarbon has a three-dimensional spiral structure with nano TiO2The particles are combined, a particle of point-shaped bulge is formed on the surface of the particles, and the particles and the bulge can cooperatively bind more rubber molecular chains to slow down the slippage phenomenon; and rutile type TiO2Has strong ultraviolet light absorbing capacity and has reinforcing and filling functions. The dual-phase nano filler provided by the invention can obviously improve the tensile strength and the elongation at break of the styrene butadiene rubber and simultaneously improve the ultraviolet resistance of the styrene butadiene rubber by only adding a small amount of the dual-phase nano filler in a carbon black reinforced styrene butadiene rubber formula system.

Description

Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber
Technical Field
The invention relates to the technical field of rubber processing, in particular to a dual-phase nano filler, a preparation method thereof and application thereof in styrene butadiene rubber.
Background
The tire is an important part for automobile production, and with the rapid development of the automobile industry, the automobile holding capacity is increased, and the requirement on the tire is increased day by day. The physical and mechanical properties, the processing property and the product use performance of the styrene butadiene rubber are close to those of natural rubber, and some properties such as wear resistance, heat resistance and vulcanization speed are better than those of the natural rubber, so that the styrene butadiene rubber is widely used for the production of tires, is the largest general synthetic rubber variety and is one of the rubber varieties which are used for realizing industrial production at the earliest.
However, pure styrene-butadiene rubber has low strength and modulus, and is often modified by blending with a reinforcing agent, wherein carbon black reinforced styrene-butadiene rubber is a widely adopted technical means. The carbon black reinforced styrene butadiene rubber takes rubber as a matrix, carbon black particles (N330, N220 and the like) as a reinforcing phase, and the carbon black plays a role in reinforcing and filling in a rubber system, so that the performance of a rubber product is improved. However, the reinforcing effect of the carbon black on the styrene butadiene rubber is still limited, and the ultraviolet resistance of the styrene butadiene rubber cannot be improved, so that the styrene butadiene rubber product cannot meet the higher quality requirement.
Disclosure of Invention
In view of the above, the present invention aims to provide a dual-phase nano filler, a preparation method thereof and an application thereof in styrene butadiene rubber. The biphase nano filler provided by the invention not only can effectively improve the mechanical property of the styrene butadiene rubber, but also can enhance the ultraviolet resistance of the styrene butadiene rubber.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a dual-phase nano filler, which comprises spiral nano carbon fibers and nano TiO discretely loaded on the surfaces of the spiral nano carbon fibers2(ii) a The nano TiO2Is in rutile type.
Preferably, the spiral diameter of the spiral nano carbon fiber is 80-100 nm; the nano TiO2The particle size of (A) is 10 to 50 nm.
Preferably, the nano TiO2The mass of the carbon nano-fiber is 30-50% of that of the spiral carbon nano-fiber.
The invention provides a preparation method of the two-phase nano-filler in the technical scheme, which comprises the following steps:
(1) carrying out heat treatment on the spiral carbon nanofibers under a vacuum condition to obtain heat-treated modified spiral carbon nanofibers; the temperature of the heat treatment is 600-700 ℃, and the vacuum degree is 10-1～10-3pa；
(2) Mixing the heat-treated modified spiral carbon nanofibers with absolute ethyl alcohol and water for ultrasonic dispersion to obtain a heat-treated modified spiral carbon nanofiber dispersion liquid;
mixing butyl titanate and absolute ethyl alcohol for ultrasonic dispersion to obtain a butyl titanate solution;
(3) mixing the heat-treated modified spiral carbon nanofiber dispersion liquid, a butyl titanate solution and glacial acetic acid for hydrothermal reaction to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is 80-100 ℃;
(4) calcining the hydrothermal reaction product to obtain the biphase nano filler; the calcining temperature is 600-700 ℃.
Preferably, the time of heat treatment in the step (1) is 2-4 h; the vacuum degree under the vacuum condition is 10-1～10-3Pa。
Preferably, the ratio of the heat-treated modified helical carbon nanofibers in the heat-treated modified helical carbon nanofiber dispersion liquid in the step (2) to absolute ethyl alcohol to water is 0.5-1 g: 80-100 mL: 3-6 mL; the volume ratio of the butyl titanate to the absolute ethyl alcohol in the butyl titanate solution is 1-3: 30-50; the ultrasonic dispersion time is independently 30-60 min.
Preferably, in the step (3), the amount ratio of the heat-treated modified spiral carbon nanofibers in the heat-treated modified spiral carbon nanofiber dispersion to the butyl titanate and glacial acetic acid in the butyl titanate solution is 0.5-1 g: 1-3 mL: 2 mL; the time of the hydrothermal reaction is 4-6 h.
Preferably, the calcining temperature in the step (4) is 600-700 ℃, and the time is 2-3 h.
Preferably, the spiral filamentous nanocarbon is prepared by a method comprising the following steps:
and carrying out chemical vapor deposition at 280-310 ℃ by taking acetylene as a carbon source and copper tartrate as a catalyst to obtain the spiral carbon nanofiber.
The invention provides the application of the dual-phase nano filler in the technical scheme or the dual-phase nano filler prepared by the preparation method in the technical scheme as a reinforcing filler in styrene butadiene rubber; the reinforcing filler further comprises carbon black; in the processing of the styrene butadiene rubber, the adding mass of the carbon black is 48-50% of the mass of the styrene butadiene rubber, and the adding mass of the dual-phase nano filler is less than or equal to 2% of the mass of the styrene butadiene rubber.
Preferably, the styrene-butadiene rubber processing comprises mixing styrene-butadiene rubber, a reinforcing filler and a processing aid and then vulcanizing.
The invention provides a dual-phase nano filler, which comprises spiral nano carbon fibers and nano TiO discretely loaded on the surfaces of the spiral 2-phase nano carbon fibers2(ii) a The nano TiO2Is in rutile type. In the present invention, the spiral filamentous nanocarbon has a three-dimensional spiral structure with nano TiO2The particles are combined to form a particle of point-shaped bulge on the surface of the spiral nano carbon fiber, and the two bulges can cooperatively bind more rubber molecular chains to slow down the slippage phenomenon; and rutile type TiO2Has strong ultraviolet light absorbing capacity and reinforcing and filling functions. Therefore, the biphase nano filler provided by the invention not only can effectively improve the mechanical property of the styrene butadiene rubber, but also can enhance the ultraviolet resistance of the styrene butadiene rubber.
The invention provides a preparation method of the dual-phase nano filler, which comprises the following steps: (1) carrying out heat treatment on the spiral carbon nanofibers under a vacuum condition to obtain heat-treated modified spiral carbon nanofibers; the temperature of the heat treatment is 600-700 ℃; (2) mixing the heat-treated modified spiral carbon nanofibers with absolute ethyl alcohol and water for ultrasonic dispersion to obtain a heat-treated modified spiral carbon nanofiber dispersion liquid; mixing butyl titanate and absolute ethyl alcohol for ultrasonic dispersion to obtain a butyl titanate solution; (3) mixing the heat-treated modified spiral nano carbon fiber dispersion liquid, a butyl titanate solution and glacial acetic acid for hydrothermal reaction to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is 80-100 ℃; (4) and calcining the hydrothermal reaction product to obtain the biphase nano filler. According to the invention, the surface active sites of the spiral carbon nanofibers are increased through heat treatment, compared with the traditional acidification treatment, the operation is simple, the use of strong acid (sulfuric acid, nitric acid and the like) is reduced, and the method is more environment-friendly; in the process of preparing the dual-phase nano filler by the hydrothermal treatment method, only two organic solvents of absolute ethyl alcohol and glacial acetic acid are used, so that the use of chemical reagents is greatly reduced, the operation is safe, and meanwhile, the appearance of impurity products can be avoided; and the temperature of the hydrothermal reaction is lower in the invention. The preparation method provided by the invention has the advantages of simple process, mild conditions and convenience in operation.
The invention provides the application of the dual-phase nano filler in the technical scheme or the dual-phase nano filler prepared by the preparation method in the technical scheme as a reinforcing filler in styrene butadiene rubber; the reinforcing filler further comprises carbon black; in the processing of the styrene butadiene rubber, the adding mass of the carbon black is 48-50% of the mass of the styrene butadiene rubber, and the adding mass of the dual-phase nano filler is less than or equal to 2% of the mass of the styrene butadiene rubber. The dual-phase nano filler provided by the invention can obviously improve the tensile strength and elongation at break of the styrene butadiene rubber and simultaneously improve the ultraviolet resistance of the styrene butadiene rubber by adding a small amount of the dual-phase nano filler in a carbon black reinforced styrene butadiene rubber formula system; compared with a styrene butadiene rubber system only added with carbon black filler, the addition of 2 percent (relative to the mass of the styrene butadiene rubber) can improve the tensile strength of the styrene butadiene rubber by 22.8 percent and the elongation at break by 12.03 percent, and the ultraviolet resistance of the rubber can be obviously improved through the test of a fluorescent ultraviolet aging test box.
Drawings
FIG. 1 shows the two-phase nano-filler TiO obtained in example 12SEM pictures of @ HCNFs;
FIG. 2 shows the two-phase nano-filler TiO of example 12XRD patterns of @ HCNFs and HCNFs;
FIG. 3 shows the fluorescence of the vulcanizates obtained by adding different fillers in example 2 and comparative example 1The effect chart of the test of the ultraviolet aging test box is that (a) in figure 3 is the comparative example 1 without adding TiO2The ultraviolet resistant effect diagram of the vulcanized rubber of @ HCNFS, (b) adding TiO for example 22The ultraviolet resistant effect diagram of the vulcanized rubber of @ HCNFs.
Detailed Description
The invention provides a dual-phase nano filler, which comprises spiral nano carbon fibers and nano TiO discretely loaded on the surfaces of the spiral nano carbon fibers2(ii) a The nano TiO2Is in rutile type.
In the invention, the spiral diameter of the spiral nano carbon fibers (HCNFs) is preferably 80-100 nm, and more preferably 85-95 nm; the nano TiO2The particle size of (A) is preferably 10 to 50nm, more preferably 35 to 45 nm. In the present invention, the nano TiO2The mass of (b) is preferably 30-50% of the mass of the spiral carbon nanofiber, and more preferably 35-45%; the nano TiO2Discretely loaded on the surface of the spiral nano carbon fiber, namely nano TiO2The surface of the spiral carbon nanofiber is distributed in discrete points.
In the present invention, the spiral filamentous nanocarbon has a three-dimensional spiral structure with nano TiO2The particles are combined to form a particle of point-shaped bulge on the surface of the spiral nano carbon fiber, and the two bulges can cooperatively bind more rubber molecular chains to slow down the slippage phenomenon; and rutile type TiO2Has strong ultraviolet light absorbing capacity and reinforcing and filling functions. Thus, the present invention provides a dual phase nanofiller (TiO)2@ HCNFs) not only can effectively improve the mechanical property of the styrene butadiene rubber, but also can enhance the ultraviolet resistance of the styrene butadiene rubber.
The invention provides a preparation method of the two-phase nano-filler in the technical scheme, which comprises the following steps:
(1) carrying out heat treatment on the spiral carbon nanofibers under a vacuum condition to obtain heat-treated modified spiral carbon nanofibers; the temperature of the heat treatment is 600-700 ℃;
(2) mixing the heat-treated modified spiral carbon nanofibers with absolute ethyl alcohol and water for ultrasonic dispersion to obtain a heat-treated modified spiral carbon nanofiber dispersion liquid;
mixing butyl titanate and absolute ethyl alcohol for ultrasonic dispersion to obtain a butyl titanate solution;
(3) mixing the heat-treated modified spiral carbon nanofiber dispersion liquid, a butyl titanate solution and glacial acetic acid for hydrothermal reaction to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is 80-100 ℃;
(4) and calcining the hydrothermal reaction product to obtain the biphase nano filler.
The invention carries out heat treatment on the spiral carbon nanofibers under the vacuum condition to obtain the heat-treated modified spiral carbon nanofibers. The invention has no special requirement on the source of the spiral nano carbon fiber, and the spiral nano carbon fiber can be prepared by a preparation method well known by the technical personnel in the field. In the embodiment of the present invention, the spiral filamentous nanocarbon is preferably prepared by a method comprising the steps of:
and carrying out chemical vapor deposition at 280-310 ℃ by taking acetylene as a carbon source and copper tartrate as a catalyst to obtain the spiral carbon nanofiber.
In the invention, the temperature of the heat treatment is 600-700 ℃, and preferably 620-660 ℃; the time of the heat treatment is preferably 2 h; the degree of vacuum of the vacuum condition is preferably 10-1～10-3Pa; the heat treatment is preferably carried out in a vacuum sintering furnace. According to the invention, a large number of active sites (some delocalized pi bonds generated on the surface of the spiral carbon nanofibers through heat treatment can enable titanium dioxide particles to land) are generated on the surface of the spiral carbon nanofibers through the heat treatment, and the points are used for subsequently loading TiO2Providing rich load points; according to the invention, the surface active sites of the spiral carbon nanofibers are increased through heat treatment, compared with the traditional acidification treatment, the operation is simple, the use of strong acid (sulfuric acid, nitric acid and the like) is reduced, and the method is more environment-friendly.
After the heat-treated modified spiral carbon nanofiber is obtained, the heat-treated modified spiral carbon nanofiber is mixed with absolute ethyl alcohol and water for ultrasonic dispersion, and a heat-treated modified spiral carbon nanofiber dispersion liquid is obtained. In the present invention, the water is preferably deionized water; the proportion of the heat-treated modified spiral carbon nanofibers in the heat-treated modified spiral carbon nanofiber dispersion liquid to absolute ethyl alcohol to water is preferably 0.5-1 g: 80-100 mL: 3-6 mL, more preferably 1 g: 100mL of: 6 mL; the time for ultrasonic dispersion is preferably 30-60 min, and more preferably 40-50 min.
According to the invention, butyl titanate and absolute ethyl alcohol are mixed for ultrasonic dispersion to obtain a butyl titanate solution. In the invention, the volume ratio of the butyl titanate to the absolute ethyl alcohol in the butyl titanate solution is preferably 1-3: 30-50, more preferably 1: 50; the time for ultrasonic dispersion is preferably 30-60 min, and more preferably 40-50 min.
After the heat treatment modified spiral carbon nanofiber dispersion liquid and the butyl titanate solution are obtained, the heat treatment modified spiral carbon nanofiber dispersion liquid, the butyl titanate solution and glacial acetic acid are mixed for hydrothermal reaction, and a hydrothermal reaction product is obtained. In the present invention, the ratio of the amount of the heat-treated modified carbon nanofibers in the heat-treated modified carbon nanofibers dispersion to the amount of the butyl titanate and the glacial acetic acid in the butyl titanate solution is preferably 0.5 to 1 g: 1-3 mL: 2mL, more preferably 1 g: 1mL of: 2 mL. In the invention, the temperature of the hydrothermal reaction is 80-100 ℃, preferably 85-95 ℃, and the time of the hydrothermal reaction is preferably 4-6 h, more preferably 4.5-5.5 h. The device for the hydrothermal reaction is not particularly required, and a hydrothermal reaction kettle which is well known to a person skilled in the art can be adopted. In the process of hydrothermal reaction, absolute ethyl alcohol is used as a cosolvent and does not participate in the reaction; taking heat treatment HCNFs as a substrate, and carrying out hydrolysis and polycondensation on active sites on the surface of the substrate to form titanium dioxide nano particles; glacial acetic acid is used as a chelating agent to slow down the hydrolysis of the butyl titanate serving as a titanium source, so that the phenomenon of overlarge particle size and agglomeration of titanium dioxide generated at the beginning of the reaction is avoided.
After the hydrothermal reaction, the invention preferably cools the obtained hydrothermal reaction liquid to room temperature, and then sequentially performs suction filtration, solid-phase washing and drying to obtain a hydrothermal reaction product. In the present invention, the solid phase washing detergent is preferably water, and the solid phase may be washed to neutrality without any particular requirement for the number of times of washing; the present invention does not require any special temperature or time for drying, and can remove moisture sufficiently.
In the process of preparing the dual-phase nano filler by the hydrothermal treatment method, only two organic solvents, namely absolute ethyl alcohol and glacial acetic acid, are used, so that the use of chemical reagents is greatly reduced, the operation is safe, and meanwhile, the appearance of impurity products can be avoided; and the temperature of the hydrothermal reaction is lower in the invention.
After a hydrothermal reaction product is obtained, the invention calcines the hydrothermal reaction product to obtain the biphase nano filler. In the invention, the calcining temperature is 600-700 ℃, preferably 630-660 ℃; the time for calcination is preferably 2-3 h, and more preferably 2.5 h. During the calcination, TiO2The crystal form is changed, and anatase type generated in the hydrothermal reaction is changed into rutile type, rutile type TiO2Has strong ultraviolet light absorbing capacity.
The preparation method provided by the invention has the advantages of simple process, mild conditions and convenience in operation.
The invention provides the application of the dual-phase nano filler in the technical scheme or the dual-phase nano filler prepared by the preparation method in the technical scheme as a reinforcing filler in styrene butadiene rubber; the reinforcing filler further comprises carbon black; in the processing of the styrene butadiene rubber, the adding mass of the carbon black is 48-50% of the mass of the styrene butadiene rubber, and the adding mass of the dual-phase nano filler is less than or equal to 2% of the mass of the styrene butadiene rubber. In the present invention, the styrene-butadiene rubber is preferably SBR 1500E; the carbon black of the present invention is not particularly limited, and carbon blacks known to those skilled in the art, such as N330 and N220, may be used. The additive added in the styrene butadiene rubber processing process has no special requirement, and can be added according to the requirement of GB/T9579-2006; in the embodiment of the invention, in the processing process of the styrene butadiene rubber, the adding sequence of the raw materials is as follows: 100 parts by mass of styrene butadiene rubber, 2 parts by mass of sulfur, 5 parts by mass of zinc oxide, 1 part by mass of stearic acid, 1.2 parts by mass of accelerator DM and 0.7 part by mass of accelerator DMM, 0.5 part by mass of accelerator DPG, 2 parts by mass of dual-phase nanofiller (TiO)2@ HCNFs), 3 parts by mass of polyethylene glycol 4000, and 48 parts by mass of carbon black.
In the present invention, the styrene-butadiene rubber processing preferably comprises vulcanizing after mixing the styrene-butadiene rubber, the reinforcing filler and the processing aid. The invention does not require any particular method for the operation of the mixing and vulcanization, and the corresponding methods known to those skilled in the art can be used. In the embodiment of the present invention, the mixing method is preferably: styrene butadiene rubber, carbon black and biphase nano filler (TiO)2@ HCNFS) and the auxiliary agent were mixed in a mixer, and the mixture was subjected to 3/4 cutters alternately at a frequency of 20 s/time, adjusted to a roll nip of 4mm, triangular wrapped 6 times, and thinly passed 6 times, and then cut to obtain a rubber compound.
And vulcanizing the rubber compound to obtain vulcanized rubber, namely the finished rubber. The invention preferably puts the rubber compound for 18h and then vulcanizes the rubber compound; the temperature of the vulcanization is preferably 160 ℃, and the time of the vulcanization is preferably 45 min.
The dual-phase nano filler provided by the invention can obviously improve the tensile strength and elongation at break of the styrene butadiene rubber and simultaneously improve the ultraviolet resistance of the styrene butadiene rubber by adding a small amount of the dual-phase nano filler in a carbon black reinforced styrene butadiene rubber formula system; compared with a styrene butadiene rubber system only added with carbon black filler, the addition of 2 percent (relative to the mass of the styrene butadiene rubber) can improve the tensile strength of the styrene butadiene rubber by 22.8 percent and the elongation at break by 12.03 percent, and the ultraviolet resistance of the rubber can be obviously improved through the test of a fluorescent ultraviolet aging test box.
The dual-phase nano-filler provided by the present invention, the preparation method thereof and the application thereof in styrene-butadiene rubber are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Biphase nano-filler TiO2Preparation of @ HCNFs:
placing spiral carbon nanofibers (HCNFs, spiral diameter of 80nm) in a vacuum sintering furnace at 600 deg.C and vacuum degree of 10-3Keeping the temperature for 2 hours under Pa to obtain heat treatment modified HCNFs;
1g of heat is addedProcessing modified HCNFs, 100mL absolute ethyl alcohol and 6mL H2Performing O ultrasonic dispersion for 30min to form a heat treatment modified spiral carbon nanofiber dispersion liquid; ultrasonically dispersing 1mL of butyl titanate and 50mL of absolute ethyl alcohol for 30min to form a butyl titanate solution;
mixing the heat-treated modified spiral carbon nanofiber dispersion liquid and butyl titanate solution, putting the mixture into a hydrothermal reaction kettle, adding 2mL of glacial acetic acid, carrying out hydrothermal reaction for 6h at 100 ℃, cooling the reaction liquid to room temperature, carrying out suction filtration, washing the obtained solid phase to be neutral, drying, and calcining for 2h at 700 ℃ to obtain the dual-phase nano filler TiO2@HCNFs。
FIG. 1 shows the two-phase nano-filler TiO obtained in example 12SEM image of @ HCNFs, from FIG. 1, it can be seen that nano TiO2The particles are uniformly distributed (distributed in discrete points) on the surface of the HCNFs in a supported manner and have uniform particle size (30-50 nm). Nano TiO 22The mass of (a) is 30% of the mass of the spiral filamentous nanocarbon.
FIG. 2 shows two-phase nano-filler TiO2XRD patterns of @ HCNFs and HCNFs, TiO can be seen from FIG. 22@ TiO contained in HCNFs2The three strong peaks (110), (211) and (101) and rutile TiO2(JCPDS patterns 21-1276) in one-to-one correspondence; the formation of rutile titanium dioxide is shown, and no other impurity peak is generated in XRD, which shows that no impurity is generated.
Example 2
The two-phase nanofiller TiO obtained in example 1 was added2The @ HCNFS and SBR1500E (styrene butadiene rubber) are mixed on a mixer according to the national standard GB/T9579-2006 with the addition of an auxiliary agent, and the specific addition sequence is as follows: 100g SBR1500E, 2g sulfur, 5g zinc oxide, 1g stearic acid, 1.2g accelerator DM, 0.7g accelerator M, 0.5g accelerator DPG, 2g TiO2@ HCNFs, 3g polyethylene glycol 4000, 48g carbon black N330, after all the materials are mixed, 3/4 cutters are alternately made at the frequency of 20 s/time, the roller spacing is adjusted to be 4mm, triangular wrapping is carried out for 6 times, and sheets are taken after passing through for 6 times to obtain TiO2@ HCNFS/carbon black/SBR 1500E mix.
Standing the rubber compound for 18h, and measuring a vulcanization curve and positive vulcanization time by using a vulcanization instrument; vulcanizing the rubber compound by using a plate vulcanizing machine, wherein the vulcanization temperature is 160 ℃, and the vulcanization time isFor 45min, TiO is obtained2@ HCNFS/carbon black N330/SBR1500E vulcanizate.
Comparative example 1
During the kneading, 2g of TiO in example 2 was added2The @ HCNFs were replaced with 2g of carbon black N330, and the rest was the same as in example 2.
The mechanical properties of the vulcanisates obtained by adding different fillers to example 2 and comparative example 1 were tested (tensile testing machine, according to GB/T528-2009), the test results are shown in table 1:
TABLE 1 mechanical Properties of vulcanizates obtained by adding different fillers to example 2 and comparative example 1
Item Tensile Strength (MPa) Elongation at Break (%)
Example 2 20.6 683.1
Comparative example 1 16.8 609.7
As can be seen from Table 1, the dual-phase nanofiller, TiO2The mechanical property of the styrene butadiene rubber can be effectively improved by adding the @ HCNFs.
The vulcanized rubber obtained by adding different fillers in example 2 and comparative example 1 is subjected to a fluorescent ultraviolet aging experimental box test under the following test conditions: the temperature is 50 +/-1 ℃, and the irradiance is 1.5W/m2The duration is 21 days; the test results are shown in FIG. 3, in FIG. 3: (a) Comparative example 1 with no TiO addition2The ultraviolet resistant effect diagram of the vulcanized rubber of @ HCNFS, (b) example 2 with the addition of TiO of example 12The ultraviolet resistant effect diagram of the vulcanized rubber of @ HCNFs. As can be seen from FIG. 3, the surface cracks of the vulcanized rubber obtained in example 2 are obviously reduced after the vulcanized rubber is irradiated by the fluorescent ultraviolet aging test chamber, which shows that the biphase nano-filler TiO2The addition of @ HCNFs improves the ultraviolet resistance of the styrene butadiene rubber.
Example 3
Biphase nano-filler TiO2Preparation of @ HCNFs:
placing HCNFs (spiral diameter is 80nm) in a vacuum sintering furnace at 600 deg.C and vacuum degree of 10-3Keeping the temperature for 2 hours under Pa to obtain heat treatment modified HCNFs;
1g of heat-treated modified HCNFs, 150mL of absolute ethanol and 8mL of H2Performing O ultrasonic dispersion for 30min to form a heat treatment modified spiral carbon nanofiber dispersion liquid; ultrasonically dispersing 4mL of butyl titanate and 50mL of absolute ethyl alcohol for 30min to form a butyl titanate solution;
mixing the heat-treated modified spiral carbon nanofiber dispersion liquid and butyl titanate solution, putting the mixture into a hydrothermal reaction kettle, adding 3mL of glacial acetic acid, reacting for 6 hours at 100 ℃, cooling the reaction liquid to room temperature, carrying out suction filtration, washing the obtained solid phase to be neutral, drying, and calcining for 2 hours at 700 ℃ to obtain the dual-phase nano filler TiO2@HCNFs。
Biphase nano-filler TiO2@ HCNFS medium nano TiO2The particles are uniformly distributed (distributed in discrete points) on the surface of HCNFS in a supported mode and have uniform particle size, and the nano TiO2The particle size of the particles is 30-50 nm and accounts for 50% of the mass of the spiral carbon nanofibers; nano TiO 22Is in rutile type.
Example 4
The two-phase nanofiller TiO obtained in example 3 was added2The @ HCNFs and SBR1500E (styrene butadiene rubber) are mixed by adding an auxiliary agent on a mixing roll according to the national standard GB/T9579-: 100g of SBR1500E, 2g of sulfur, 5g of zinc oxide, 1g of stearic acid, 1.2g of accelerator DM, 0.7g of accelerator M, 0.5g of accelerator DPG, 2g of TiO2@ HCNFs, 3g polyethylene glycol 4000, 48g carbon black N330, all materials mixed in, 2Alternately using 3/4 cutters at a frequency of 0 s/time, adjusting roll spacing to 4mm, packaging for 6 times, passing through for 6 times, and slicing to obtain TiO2@ HCNFS/carbon black N330/SBR1500E rubber compound.
Standing the rubber compound for 18h, and measuring a vulcanization curve and positive vulcanization time by using a vulcanization instrument; vulcanizing the rubber compound by using a plate vulcanizing machine, wherein the vulcanization temperature is 160 ℃, and the vulcanization time is 45min to obtain TiO2@ HCNFS/carbon black N330/SBR1500E vulcanizate.
Comparative example 2
During the kneading, 2g of TiO in example 4 was added2The @ HCNFs were replaced with 2g of carbon black N330, and the rest was the same as in example 4.
The mechanical properties (tensile testing machine, according to GB/T528-2009) of the vulcanized rubbers obtained by adding different fillers in example 4 and comparative example 2 were tested, and the test results are shown in Table 2:
TABLE 2 mechanical Properties of vulcanizates obtained by adding different fillers to example 4 and comparative example 2
Item Tensile Strength (MPa) Elongation at Break (%)
Example 4 20.1 627
Comparative example 2 17.3 587.2
As can be seen from Table 2, bisPhase nano-filler TiO2The mechanical property of the styrene butadiene rubber can be effectively improved by adding the @ HCNFs.
The vulcanized rubber obtained by adding different fillers in example 4 and comparative example 2 is subjected to a fluorescent ultraviolet aging experimental box test under the following test conditions: the temperature is 50 +/-1 ℃, and the irradiance is 1.5W/m2The duration is 21 days; and (3) testing results: compared with the comparative example 2, the surface cracks of the vulcanized rubber obtained in the example 4 are obviously reduced after the vulcanized rubber is irradiated by the fluorescent ultraviolet aging test chamber, which shows that the biphase nano-filler TiO is2The addition of @ HCNFs improves the ultraviolet resistance of the styrene butadiene rubber.
The embodiments show that the two-phase nano filler provided by the invention can obviously improve the tensile strength and elongation at break of the styrene butadiene rubber and simultaneously improve the ultraviolet resistance of the styrene butadiene rubber by adding a small amount of the two-phase nano filler in a carbon black reinforced styrene butadiene rubber formula system; the preparation process is simple, the conditions are mild, and the operation is convenient
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. The dual-phase nano filler is characterized by comprising spiral nano carbon fibers and nano TiO discretely loaded on the surfaces of the spiral nano carbon fibers2(ii) a The nano TiO2Is in the rutile type; the preparation method of the dual-phase nano filler comprises the following steps:
(1) carrying out heat treatment on the spiral carbon nanofibers under a vacuum condition to obtain heat-treated modified spiral carbon nanofibers; the temperature of the heat treatment is 600-700 ℃;
(2) mixing the heat-treated modified spiral carbon nanofibers with absolute ethyl alcohol and water for ultrasonic dispersion to obtain a heat-treated modified spiral carbon nanofiber dispersion liquid;
mixing butyl titanate and absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a butyl titanate solution;
(3) mixing the heat-treated modified spiral carbon nanofiber dispersion liquid, a butyl titanate solution and glacial acetic acid for hydrothermal reaction to obtain a hydrothermal reaction product; the dosage ratio of the heat treatment modified spiral carbon nanofibers in the heat treatment modified spiral carbon nanofiber dispersion liquid to the butyl titanate and the glacial acetic acid in the butyl titanate solution is 0.5-1 g: 1-3 mL: 2 mL; the temperature of the hydrothermal reaction is 80-100 ℃;
(4) and calcining the hydrothermal reaction product to obtain the biphase nano filler.
2. The dual-phase nanofiller according to claim 1, wherein the helical nanocarbon fibers have a helix diameter of 80 to 100 nm; the nano TiO2The particle size of (A) is 10 to 50 nm.
3. The dual-phase nanofiller according to claim 1 or 2, characterized in that said nano TiO is2The mass of the carbon nano-fiber is 30-50% of that of the spiral carbon nano-fiber.
4. A method for preparing a dual-phase nanofiller as claimed in any one of claims 1 to 3, comprising the steps of:
(1) carrying out heat treatment on the spiral carbon nanofibers under a vacuum condition to obtain heat-treated modified spiral carbon nanofibers; the temperature of the heat treatment is 600-700 ℃;
(2) mixing the heat-treated modified spiral carbon nanofibers with absolute ethyl alcohol and water for ultrasonic dispersion to obtain a heat-treated modified spiral carbon nanofiber dispersion liquid;
mixing butyl titanate and absolute ethyl alcohol for ultrasonic dispersion to obtain a butyl titanate solution;
(3) mixing the heat-treated modified spiral carbon nanofiber dispersion liquid, a butyl titanate solution and glacial acetic acid for hydrothermal reaction to obtain a hydrothermal reaction product; the temperature of the hydrothermal reaction is 80-100 ℃;
(4) and calcining the hydrothermal reaction product to obtain the biphase nano filler.
5. The preparation method according to claim 4, wherein the time of the heat treatment in the step (1) is 2-4 h; the vacuum degree under the vacuum condition is 10-1～10-3Pa。
6. The preparation method according to claim 4, wherein the ratio of the heat-treated modified helical carbon nanofibers in the heat-treated modified helical carbon nanofiber dispersion liquid in the step (2) to absolute ethyl alcohol to water is 0.5-1 g: 80-100 mL: 3-6 mL;
the volume ratio of the butyl titanate to the absolute ethyl alcohol in the butyl titanate solution is 1-3: 30-50; the ultrasonic dispersion time is independently 30-60 min.
7. The method according to claim 4, wherein in the step (3), the ratio of the amount of the heat-treated modified carbon nanofibers in the heat-treated modified carbon nanofibers dispersion to the amount of the butyl titanate and the glacial acetic acid in the butyl titanate solution is 0.5 to 1 g: 1-3 mL: 2 mL; the time of the hydrothermal reaction is 4-6 h.
8. The preparation method according to claim 4, wherein the calcining temperature in the step (4) is 600-700 ℃ and the calcining time is 2-3 h.
9. Use of the dual-phase nanofiller according to any one of claims 1 to 3 or the dual-phase nanofiller prepared by the preparation method according to any one of claims 4 to 8 as a reinforcing filler in styrene butadiene rubber; the reinforcing filler further comprises carbon black; in the processing of the styrene butadiene rubber, the adding mass of the carbon black is 48-50% of the mass of the styrene butadiene rubber, and the adding mass of the dual-phase nano filler is less than or equal to 2% of the mass of the styrene butadiene rubber.
10. The use of claim 9, wherein the styrene butadiene rubber processing comprises compounding styrene butadiene rubber, reinforcing filler and processing aid followed by vulcanization.
CN202011213695.3A 2020-11-04 2020-11-04 Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber Active CN112300444B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011213695.3A CN112300444B (en) 2020-11-04 2020-11-04 Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011213695.3A CN112300444B (en) 2020-11-04 2020-11-04 Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber

Publications (2)

Publication Number Publication Date
CN112300444A CN112300444A (en) 2021-02-02
CN112300444B true CN112300444B (en) 2022-05-17

Family

ID=74324790

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011213695.3A Active CN112300444B (en) 2020-11-04 2020-11-04 Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber

Country Status (1)

Country Link
CN (1) CN112300444B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114044939B (en) * 2021-11-01 2023-03-31 山东理工大学 Preparation method of high-dispersion anti-aging nano filler for tire

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683710B (en) * 2012-05-21 2014-08-20 北京化工大学 Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof
CN103866389B (en) * 2014-02-17 2016-02-03 南京大学昆山创新研究院 Porous monocrystalline nanometer sheet TiN preparation method and purposes on a kind of carbon fiber
CN106431186B (en) * 2016-09-05 2019-03-29 北京工业大学 A kind of fiber-loaded rutile TiO2Composite S iO2The preparation method of aeroge
CN109103029B (en) * 2018-08-27 2020-12-11 四川理工学院 Spiral nano carbon fiber/TiO2Composite material and use thereof
CN110318252B (en) * 2019-08-16 2021-09-28 四川轻化工大学 Composite material with spiral carbon nanofiber surface loaded with zinc oxide particles and preparation method and application thereof

Also Published As

Publication number Publication date
CN112300444A (en) 2021-02-02

Similar Documents

Publication Publication Date Title
CN110318252B (en) Composite material with spiral carbon nanofiber surface loaded with zinc oxide particles and preparation method and application thereof
JPWO2004009711A1 (en) Modified calcium carbonate, polymer composition containing the same, and production method thereof
CN108864773B (en) Modified spiral carbon nanofiber, preparation method and application thereof, and rubber composite material
JP4522689B2 (en) Rubber composition containing inorganic reinforcing agent
Zhao et al. Tannic acid-assisted green fabrication of functionalized graphene towards its enhanced compatibility in NR nanocomposite
TW200734387A (en) Process for preparing organically modified layered double hydroxide
CN109161110A (en) A kind of addition graphene/carbon black composite material tyre airtight layer glue and preparation method thereof
CN101395013A (en) Tyre and crosslinkable elastic composition
CN105694104B (en) A kind of preparation method of rubber nano-calcium carbonate
CN108219392B (en) Plastic auxiliary agent with ultraviolet aging resistance and moisture retention functions as well as preparation method and application thereof
CN112300444B (en) Biphase nano filler, preparation method thereof and application thereof in styrene butadiene rubber
CN113861459B (en) Spiral carbon nanofiber reinforced rubber composite material and preparation method thereof
KR101964136B1 (en) Process for preparing wet master-batch from mixture of styrene-butadiene rubber and surface-modified silica
CN106883517A (en) A kind of reinforced plastics woven bag material
Lin et al. Reactivity of sulfide-containing silane toward boehmite and in situ modified rubber/boehmite composites by the silane
KR100700624B1 (en) Preparation of neodymium carbon nanotube and 1,4-butadiene polymerization using it
WO2022205791A1 (en) Graphene modified pet film material and preparation method therefor
EP2377694B1 (en) Rubber composition containing treated silica, method of manufacturing and product with component thereof
WO2022125675A1 (en) Methods of preparing a composite having elastomer and filler
CN109957121B (en) Preparation method of nano composite material and preparation method of vulcanized rubber
CN107555460A (en) A kind of Nano calcium carbonate dedicated preparation method of rubber tyre
JP2020530872A (en) Rubber composition for tires containing carbon nanotubes and its manufacturing method
Bu et al. Fabrication and characterization of optically active polyacetylene@ WO3 nanorodhybrids with low infrared emissivity
CN109206755A (en) A kind of spectacle-frame attapulgite-active calcium silicate modified EPT rubber composite material preparation method
CN112778584A (en) Rubber composite master batch and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant